Arylaminoanthraquinone dyestuffs and process of making same.



UNITED STATES PATENT OFFICE. i

GEQBG KRANZLEIN, 0F LINDLINGEN, NEAR; HQQHST-ON-THE MAIN, RUDOLE HAGEN- BACK, OF FRANKFORT-ON-THE-MAIN, AND FZEANZ. GILOY, 0F HdCHST-ON-CDHE- MAIN, GERMANY, ASSIGNORS TO FARBWERKE VOBII MEISTER LUCIUS & BBfiNING, 0F HtjCHST-ON-THE-MAIN, GERMANY, A COBQQWOJSI O1 GERMANY.

ARYLAMIT OANTHRAQUINQNE DYESTUFFS AND PBDQESS OF MAKING SAME.

No Drawing.

To all 'lO/LOl/t it may concern Be it known that We, GEono KRKNZ EIN, Ph. 1)., RK'DOLF llxonxnxcn, Ph. D., and Fnxx'lz GiLoY, P11. 1)., citizens of the Empire of Germany, residing at Lindlingen, near Hochst on the Main, Frankfort on the- Main, and ll ichst-onthe-Main, Germany, respectively, have invented certain new and useful Improvements in Arylaminoanthraquinone Dyestuffs and Processes of Making Same, Of which the following is a specification.

We have found that valuable arylaminoanthraquinones which. in the form of their sulfonic acids constitute acid wool-dye stulfs, remarkablfor their absolute fastness to potting and tor. their great tinctorial power, are obtained by intro ucing negative groups--under which we comprise a nitro group or any halogeninto anthraquinone derivatives of the general formula:

wherein A stands for a substituted or nonsubstituted anthraquinone residue and X for an aromatic residue containi l p one or more aryl groups, and wherein O :N are in .1 2 z 3 position, condensing the products thus obtained with aromatic amins and, if required, sulfonating these Condensation, prod.- ucts.

The new wool-dyestuffs of the an thrar quinone series constitute sulfonic acids of bodies of the general formula:

0 R.NH.A(OH) \X, V

wherein R stands for an aryl, X for an arcmatic residue and A for the authraquinone residue. As parent materials there may be usedfor this reaction the oxazoles or oxazins derived from B-amindalizarin.

The following examples illustrate our invention, the parts being by weight:

Example I: 10 parts of the nitro derivative, obtainable by treating the oxazole de rived from S-aminoalizarin and benzoylchlorid with one molecular proportion of nitric acid. are heated to boiling for about one hour with 100 parts of p-toluidin and then treated in the usual manner with al- Specification of Letters Patent.

. mone bluish tint.

PatentedMay'll, 1915.

Application filed May 13, 1914A Serial R0. 838,292.

20 parts of the condensation products thus obtained are then introduced and stirred at ordinary temperature into a mixture of 100 parts of concentrated sulfuric acid and 100 parts of oleum of 25% strength; this mixture is allowed to stand for a day and is pressed uponeice. The paste thus obtained after being filtered, is washed with a diluted solution of common salt until it becomes neutnali and then dried. The resulting sulfoulc acids dye wool in an acid bath fast violet. tints, the dyestufi, obtained when using p-toluidin, showing a considerably The violet dyeings on being subsequently chromed turn green; they are nemarkable for their excellent fast mess to. milling, washing and potting and to light. The said wool-dyestufi' obtained by using p-toluidin has the following constitut1on:

on /C0\ /;p i ca1. c., H eets,

NH-oancn, sole.-

We have furthermore found that similar dyestuffs may be obtained by introducing acid residues into sulfonicacids of the aforesaid oxazole, and subjecting the products thus obtained to reaction with aromatic amins, the resulting bodies being distinguished from the above described sulfonated products by the fact that their sulfonic group is in another nucleus.

Example ll: 10 parts of the oxazole obtainable from benzoylchlorid and i-amino alizarin are sulfonatcd at llO-ISO C. with 100 parts of olcum of 90 per cent. strength;

after cooling. 5 parts of water are'carefullv stirred for some hours at ordinary temperature. The whole is then poured into a cold aqueoiis solution of a sufiicient quantity of p-tolui'din sulfate, for the purpose of pro- 5 ducing the p-toluidin salt from the sulfonic acid, the mass filtered off, washed with a small quantity of water and centrifugated or pressed. parts of the dry nitrosulfonic acid thus obtained are carefully heat- 10 ed with 100 parts of p-toluidin and subsequently boiled for two hours. After cool ing, the mass is finally treated with warm diluted hydrochloric acid and the dyestuff thus produced'is filtered and washed with water. Thus the dyestuff is obtained as an indigo-blue powder, it being advantageous to convert it into its sodium salt and, if required, crystallize it from water. Instead of the nitrated sulfonic acid the halogenated 0 acid may be employed, whereas for the p-toluidin any other aromatic amin may be substituted.

The dyestuff produced according to the foregoing example has most probably the constitution \V e have finally found that the reaction as above set forth may be applied generally and thus dyestuffs of similar valuable properties obtained, by synthetizing such dyestuffs as contain in 2.3 position a substituted benzoxazole nucleus or any other heterocvelic rings derived from [i-aminoalizarin.

Example III: 20 parts of the nitrated oxazole which latter is obtained from o-chlorobenzoylchlorid and fi-aminoalizarin, and has the formula:

on l 0 L \i Q are heated to boiling with 150 parts of p-toluidin; when the reaction is complete,

the fusion after being cooled to 100 C. is

diluted with 150 parts of alcohol. whereupon the mass is filtered off and washed with alcohol. By sulfonating the violet color-base thus obtained, a sulfonic acid is produced which as regards the tint it dyes and its fastness is quite similar to the dyestufi' referred to in the foregoing Example I. A dyestufi' which as regards its tinctorial properties is almost identical with that just described, is obtained by substituting for the oxazole as above defined that derived from 2.4-dinitrobenzoylchlorid and (i-aminoalizarin. i

Example IV: 20 parts of the nitroderiva' tive of the condensation product which is formed by heating equivalent quantities of @amiimalimrin and benzoin in naphthalene whereby water is eliminated, and to which the formula:

may be attributed, are treated as indicated in Example 111 with ptohu lin and worked up. The violet color-base thus produced, after being sulfonated. yields a dyestufi' I which regarding the tint it dyes and its so fastness is quite analogous to that described in Example II.

Example V: 20 parts of the nitroderivati e of the condensation product which is formed by heating equivalent quantities of fi-aminoalizarin and bromacetophenone in naphthalene whereby Water and hydrobromic acid are eliminated, and to which the formula:

we claim is:

1. The process of manufacturing new arylaminoanthraquinone dyestuffs, which consists in introducing acid groups into anthraquinone derivatives of the general formula wherein A means an anthraquinone residue, and X an aromatic residue, and OII:O:N stand in 1:2:3 position, then condensing the products thus obtained with aromatic amins.

2. The process of manufacturing new arylaminoanthraquinone dyestuffs, which consists in introducing acid groups into anthraquinone derivatives of the general formula:

O A(OH) N X wherein A means an anthraquinone residue, and X an aromatic residue, and ()H:O:N stand in 1:2:3 position, then condensing the products thus obtained with aromatic amins. and sulfonating these condensation products. 7

3. The process of manufacturing new arylaminoanthraquinone dyestuffs, which consists in introducing negative groups into 4. The process of numufacturing new arylaminoanthraquinone dyestufis, .which consists in introducing ajnitrotgroup into anthraquinonc derigntivfisisgfl f general ,;...q formula: 7

song-1x wherein A means .anthraquinone residue, and X aromatic residue, 'and OH:O:N stand in 1:23 'tion,' condensing the products thus obtained with aromatic amins and sulf onatin'g these condensation prodnets 4 I I 5. The pr pf manufacturing new a laminoanthraqumone dyestuffs, which co isists iin nitrating the, oxazole' derived from (i-al ninoaljzarin and a benzoic acid derivativefpondensing the nitro product with emetic amin's and"'sulfonatmg the conensation products. -.6. -'1 hei process of manufacturing new iarylaminoaijithraquinone dyestufis, which consistsdxi'nitrating the oxazole derived e from H-ami'noalizarin and a benzoic acid derivative condensing the nitro product with p-toluidin and sulfona-ting the condensation products-f. 1

7. As'new products, the acid wool-dye- 40 studs of the anthraquinone series, being sulfonic acids of products of the general formule: M O R.-NH.A(OH) X v WheriniR stands for an aryl group, X for an aromatic residue and A for an anthraquinone residue, which are soluble in water to a violet solution from which they dye wool violet tints which turn green on being uently treated with chrome.

s new products, the acid wool-dyestuffs of the anthraquinone series, being sulfonic acids of products of the general formula:

subse wherein R and Ar stand for an aryl-group and A for an ,anthraquinone residue, which .are soluble in water to 'a violet solution from which they dye wool violet tints which turn green on being subsequently treeted with chrome. I

9. As new products, the acid wool-dyestuffs of the anthraquinone series, being siuL orfonic acids 0t products of the genera mula:

which is an indigo-blue powder, soluble in water to a violet solution from which it dyes wool violet tints which turn green on being subsequently treated with chrome.

In testimony whereof, We afiix our signatures in presence of two witnesses.

GEORG KRANZLEIN. RUDOLF HAGENBAGH. FRANZ GILOY.

Witnesses:

JEAN GRUND, CARL GRUND. 

